Heterocyclic compounds as fungicides

ABSTRACT

Fungicidally active compounds of the formula ##STR1## and stereoisomers thereof, wherein A is the group ═CW-- or a nitrogen atom, B is the group ═CX-- or a nitrogen atom, D is the group ═CY-- or a nitrogen atom, and E is the group ═CZ-- or a nitrogen atom, wherein W, X, Y and Z, which may be the same or different, are, for example, hydrogen, halogen, nitro, nitrile, or other defined groups and wherein R 1  and R 2  are alkyl, cycloalkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted aralkyl, cycloalkyl groups, or optionally substituted heteroaromatic, and V is oxygen or sulfur.

This is a division of application Ser. No. 07/442,436, filed Nov. 24,1989, now U.S. Pat. No. 5,091,407, which is a continuation of Ser. No.06/872,687, filed Jun. 10, 1986, now abandoned.

This invention relates to derivatives of acrylic acid useful asfungicides, to processes for preparing them, to fungicidal compositionscontaining them, and to methods of combating fungi, especially fungalinfections in plants, using them.

The invention provides a compound having the general formula (I):##STR2## and stereoisomers thereof, wherein A is the group ═CW-- or anitrogen atom, B is the group ═CX-- or a nitrogen atom, D is the group═CY-- or a nitrogen atom, and E is the group ═CZ-- or a nitrogen atom,wherein W, X, Y and Z, which may be the same or different, are hydrogenor halogen atoms, or nitro, nitrile, the group ##STR3## or any of thefollowing, optionally substituted groups namely alkyl, cycloalkyl,cycloalkylalkyl, alkenyl, alkynyl, aryl, aralkyl, arylazo, alkoxy,heterocyclyloxy, aryloxy, aryloxyalkyl, amino, acylamino or the groupsCO₂ R³, CONR⁴ R⁵, COR⁶ or S(O)_(n) R⁷ (where n=0, 1, or 2) or CR⁸ ═NR⁹ ;and wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸, which may be the same ordifferent, are hydrogen atoms, but R¹ and R² are not hydrogen, or alkyl,cycloalkyl, alkenyl, alkynyl, optionally substituted aryl, optionallysubstituted aralkyl, cycloalkyl groups or optionally substitutedheteroaromatic (which can contain O, N or S atoms in a 5 or 6 memberedring e.g. thiophene, furan, pyridyl or pyrimidinyl), whilst R⁹ may bealkyl, cycloalkyl optionally, substituted aryl, optionally substitutedaralkyl or cycloalkylalkyl or optionally substituted aromaticheterocyclyl. V can be either oxygen or sulphur.

The compounds of the invention contain at least one carbon-carbon doublebond, and are sometimes obtained in the form of mixtures of geometricisomers. However, these mixtures can be separated into individualisomers, and this invention embraces such isomers individually and asmixtures.

A, B, E, and D are groups which, taken together with the N-atom,constitute a pyrrole, pyrazole, imidazole, triazole or tetrazole ring.

Preferred alkyl groups for W, X, Y, Z and R¹ to R⁹ contain from 1 to 6,especially 1 to 4, carbon atoms, and can be straight or branched chainalkyl groups having 1 to 6, e.g. 1 to 4 carbon atoms; examples aremethyl, ethyl, propyl (n- or iso-propyl) and butyl (n-, sec-, iso- ort-butyl).

R¹ and R² are preferably both methyl.

Preferred cycloalkyl groups for R¹ to R⁹ contain from 3 to 6 carbonatoms, e.g. cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.Preferred alkenyl and alkynyl groups for R¹ to R⁸ and W, X, Y and Zcontain up to 7 carbon atoms and preferably up to 4 carbon atoms; andinclude allyl and propargyl.

When any of W, X, Y and Z, and R¹ to R⁹ are, or include, aryl, e.g.phenyl, it may be unsubstituted, or substituted with 1, 2 or 3 ringsubstituents at the 2-, 3- or 4 positions of the ring which may be thesame or different. Examples of aryl groups are phenyl, 2-, 3-, or4-chlorophenyl, 2,4- or 2,6-dichlorophenyl, 2,4- or 2,6-difluorophenyl,2-, 3- or 4-fluorophenyl, 2--, 3- or 4-bromophenyl, 2 -, 3- or4-methoxyphenyl, 2,4-dimethoxyphenyl, 2-, 3 - or 4 -ethoxyphenyl, 2-fluoro-4-chorophenyl, 2-chloro-4-fluorophenyl, 2-, 3- or 4-methylphenyl,2-, 3- or 4-ethylphenyl, 2-, 3- or 4-trifluoromethylphenyl,4-phenyl-phenyl (4-biphenylyl) , 2-chloro-4-methoxyphenyl,2-fluoro-4-methoxyphenyl, 2-chloro-4-methylphenyl, 2-fluoro-4-methylphenyl, 4-isopropylphenyl.

When R⁹ is cycloalkylalkyl it may be, for example, comprised of anycycloalkyl moiety containing from 3 to 6 carbon atoms combined with analkyl moiety containing from 1 to 6 carbon atoms and specific cycloalkyland alkyl moieties are those specified above.

In a further aspect the invention provides compounds according togeneral formula I wherein W, X, Y and Z are hydrogen, halogen, nitro,nitrile, C₁₋₄ alkyl, C₃₋₆ alkenyl, C₃₋₆ alkynyl, aryl , aryl₁₋₄ alkyl ,arylazo, C₁₋₄ alkoxy, heterocyclyloxy, aryloxy, aryloxyC₁₋₄ alkyl, orCOOR³, CONR4R⁵ COR⁶, or S(O)_(n) R⁷ where n is 0, 1 or 2, or CR⁷ ═NR⁸wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ are C₁₋₄ alkyl , C₃₋₆ cycloalkyl,C₃₋₄ alkenyl, C₃₋₄ alkynyl, or are an optionally substituted group whichis aryl, aryl C₁₋₄ alkyl, C₃₋₆ cycloalkyl, pyrrole, imidazole, pyrazole,1,2,3-triazole, 1,2,4-triazole or tetrazole, and R⁹ is C₁₋₄ alkyl, C₃₋₆cycloalkyl or an optionally substituted group which is aryl arylC₁₋₄alkyl, or C₃₋₆ cycloalkylC₁₋₄ alkyl; and V is oxygen.

In a yet further aspect the invention provides compounds having thegeneral formula I wherein R¹ and R² are both methyl and the moiety:##STR4## is a substituted ring which is a pyrrole, imidazole, pyrazole,1,2,3-triazole, 1,2,4-triazole, or 1,3,4-triazole ring.

In a still further aspect the invention provides compounds having thegeneral formula I wherein R¹ and R² are both methyl and the moiety:##STR5## is a pyrrole, imidazole, pyrazole, 1,2,3-triazole,1,2,4-triazole, or 1,3,4-triazole ring; and wherein E is a carbon atombearing directly, or through a linking group which is --CH═CH--, --CO--,═CH--, --S--, --SO--, --O--CO--, --CH₂ --O--, --O--CH₂ --, --O--CH₂--CO--, --CH₂ -- or --CH₂ --CH₂ --; any of cyano (i.e. CN), C₁₋₄ alkyl,halogen, nitro, phenyl; pyridyl, thienyl, pyrrol and piperidine alloptionally substituted with C₁₋₄ alkyl, C₁₋₄ alkoxy, halogen, haloC₁₋₄alkyl, C₃₋₆ cycloalkyl, C₃₋₆ cycloalkenyl, or biphenylyl.

In another aspect the invention provides compounds having the formula:##STR6## wherein A is ═CH--, or ═N--, D is ═CH-- or ═N--; and Z is cyano(i.e. CN), C₁₋₄ alkyl, halogen, nitro, phenyl, pyridyl, thienyl,pyrrolyl or piperidine all optionally substituted with C₁₋₄ alkyl, C₁₋₄alkoxy, halogen, haloC₁₋₄ alkyl, C₃₋₆ cycloalkyl, C₃₋₆ cycloalkenyl, orbiphenylyl; the group Z being linked directly to the ring carbon atom orthrough --CH═CH--, --CO--, ═CH--, --S--, --SO--, --O--CO--, --CO--O--,--O--CH₂ --, --O--CH₂ --CO--, --CH₂ --, or --CH₂ --CH₂ --, thereto.

In yet another aspect the invention provides compounds having theformula: ##STR7## wherein X is CN, C₁₋₄ alkoxy carbonyl, phenacylwherein the phenyl ring thereof is optionally substituted at the 2- , 3-or 4-position with halogen, C₁₋₄ alkyl, or haloC₁₋₄ alkyl, styryl,theinylcarbonyl, or pyridylthio; and Y is hydrogen, C₁₋₄ alkyl, ornitro.

In particular the invention provides the compounds having the structuralformula: ##STR8##

                                      TABLE I                                     __________________________________________________________________________    Compound                          Melting                                     No.   R.sup.1                                                                          R.sup.2                                                                          X           Y   Z     point (°C.)                                                                  olefinic*                                                                          isomer.sup.+                     __________________________________________________________________________    1     CH.sub.3                                                                         CH.sub.3                                                                         2-( .sub.-- EC.sub.6 H.sub.5 CHCH)                                                        H   H     126-128                                                                             7.71 Z                                2     CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 CO                                                                      H   H     78-79 7.49 Z                                3     CH.sub.3                                                                         CH.sub.3                                                                         2-CN        H   H     97    7.67 Z                                4     CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 CH.sub.2                                                                H   H                Z                                5     CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.5 H.sub.11                                                                        H   H                Z                                6     CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 CH.sub.2 CH.sub.2                                                       H   H                Z                                7     CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 N(Me)CO                                                                 H   H                Z                                8     CH.sub.3                                                                         CH.sub.3                                                                          ##STR9##   H   H                Z                                9     CH.sub.3                                                                         CH.sub.3                                                                         3-C.sub.6 H.sub.5 CO                                                                      H   H     Oil   7.57 Z                                10    CH.sub.3                                                                         CH.sub.3                                                                         2-(4-ClC.sub.6 H.sub.4 CO)                                                                H   H     127-128                                                                             7.55 Z                                11    CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 CO                                                                      5-CH.sub.3                                                                        H     77-80 7.58 Z                                12    CH.sub.3                                                                         CH.sub.3                                                                         2-(4-CH.sub.3 OC.sub.6 H.sub.4 CO)                                                        H   H     116   7.46 Z                                13    CH.sub.3                                                                         CH.sub.3                                                                         2-(2,4-Cl.sub.2 C.sub.6 H.sub.3 CO)                                                       H   H     124-125                                                                             7.48 Z                                14    CH.sub.3                                                                         CH.sub.3                                                                         2-(4-FC.sub.6 H.sub.4 CO)                                                                 H   H     74    7.45 Z                                15    CH.sub.3                                                                         CH.sub.3                                                                         2-(2-FC.sub.6 H.sub.4 CO)                                                                 H   H     Oil   7.46 Z                                16    CH.sub.3                                                                         CH.sub.3                                                                         2-(4-.sup.t C.sub.4 H.sub.9 C.sub.6 H.sub.4 CO)                                           H   H     111   7.46 Z                                17    CH.sub.3                                                                         CH.sub.3                                                                         2-(4-CF.sub.3 C.sub.6 H.sub.4 CO)                                                         H   H     127   7.55 Z                                18    CH.sub.3                                                                         CH.sub.3                                                                         2-(2-C.sub.5 H.sub.4 NS)                                                                  H   H     79    7.53 Z                                19    CH.sub.3                                                                         CH.sub.3                                                                         2-(2-C.sub.5 H.sub.4 NSO)                                                                 H   H     157-159    Z                                20    CH.sub.3                                                                         CH.sub.3                                                                         2-CH.sub.3 OCO                                                                            H   H     76-78 7.50 Z                                21    CH.sub.3                                                                         CH.sub.3                                                                         2-.sup.t C.sub.4 H.sub.9 CO                                                               H   H     Oil   7.40 Z                                22    CH.sub.3                                                                         CH.sub.3                                                                         2-(4-CH.sub.3 C.sub.6 H.sub.4 CO)                                                         H   H     117-118                                                                             7.46 Z                                23    CH.sub.3                                                                         CH.sub.3                                                                         2-(2-ClC.sub.6 H.sub.4 CO)                                                                H   H     Oil   7.46 Z                                24    CH.sub.3                                                                         CH.sub.3                                                                         2-(2-C.sub.4 H.sub.3 SCO)                                                                 H   H     81-83 7.47 Z                                25    CH.sub.3                                                                         CH.sub.3                                                                         2-(3,5-Cl.sub.2 C.sub.6 H.sub.3 CO)                                                       H   H     143-144    Z                                26    CH.sub.3                                                                         CH.sub.3                                                                         2-(2,6-Cl.sub.2 C.sub.6 H.sub.3 CO)                                                       H   H     96-97 7.57 Z                                27    CH.sub.3                                                                         CH.sub.3                                                                         2-(3-FC.sub.6 H.sub.4 CO)                                                                 H   H     Oil   7.44 Z                                28    CH.sub.3                                                                         CH.sub.3                                                                         2-(3-ClC.sub.6 H.sub.4 CO)                                                                H   H     108   7.44 Z                                29    CH.sub.3                                                                         CH.sub.3                                                                         2-.sup.n C.sub.3 H.sub.7 OCO                                                              H   H     Oil   7.50 Z                                30    CH.sub.3                                                                         CH.sub.3                                                                         2-.sup.t C.sub.4 H.sub.9 OCO                                                              H   H     Oil   7.37 Z                                31    CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 CH.sub.2 OCO                                                            H   H                Z                                32    CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 OCO                                                                     H   H                Z                                33    CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 COCO                                                                    H   H                Z                                34    CH.sub.3                                                                         CH.sub.3                                                                         2-(2-C.sub.4 H.sub.3 OCO)                                                                 H   H     85-6  7.50 Z                                35    CH.sub.3                                                                         CH.sub.3                                                                         2-(2-C.sub.5 H.sub.5 NCO)                                                                 H   H                Z                                36    CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 S                                                                       H   H                Z                                37    CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 CO                                                                      H   5-CN             Z                                38    CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 CO                                                                      H   5-CO.sub.2 CH.sub.3                                                                            Z                                39    CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.5 H.sub.10 NCH.sub.2                                                              H   H                Z                                40    CH.sub.3                                                                         CH.sub.3                                                                         2-(3-CH.sub.3 C.sub.6 H.sub.4 CO)                                                         H   H     110-1 7.51 Z                                41    CH.sub.3                                                                         CH.sub.3                                                                         2-(4-FC.sub.6 H.sub.4 CH.sub.2)                                                           H   H                Z                                42    CH.sub.3                                                                         CH.sub.3                                                                         2-(4-FC.sub.6 H.sub.4 CH.sub.2 CH.sub.2)                                                  H   H                Z                                43    CH.sub.3                                                                         CH.sub.3                                                                         2-(3-C.sub.4 H.sub.3 SCO)                                                                 H   H     130-1 7.50 Z                                44    CH.sub.3                                                                         CH.sub.3                                                                         2-(3-C.sub.4 H.sub.3 OCO)                                                                 H   H                Z                                45    CH.sub.3                                                                         CH.sub.3                                                                         2-(3-C.sub.5 H.sub.4 NCO)                                                                 H   H                Z                                46    CH.sub.3                                                                         CH.sub.3                                                                         2-[2-(5-ClC.sub.5 H.sub.3 N)CO]                                                           H   H                Z                                47    CH.sub.3                                                                         CH.sub.3                                                                         4-FC.sub.6 H.sub.5 OCO                                                                    H   H                Z                                48    CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 OCH.sub.2                                                               H   H                Z                                49    CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 CHCH.sub.3                                                              H   H                Z                                50    CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.3 H.sub.7 CHCH.sub.3                                                              H   H                Z                                51    CH.sub.3                                                                         CH.sub.3                                                                         2-(CH.sub.3).sub.2 CHOCO                                                                  H   H                Z                                52    CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 CO                                                                      3CH.sub.3                                                                         H                Z                                53    CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 CO                                                                      4CH.sub.3                                                                         H                Z                                54    CH.sub.3                                                                         CH.sub.3                                                                         2-(3-CH.sub.3 OC.sub.6 H.sub.4 CO)                                                        H   H     92-3  7.53 Z                                55    CH.sub.3                                                                         CH.sub.3                                                                         H           H   H     88-9  7.51 Z                                56    CH.sub.3                                                                         CH.sub.3                                                                         2-[3-(6-ClC.sub.5 H.sub.3 N)CO]                                                           H   H                Z                                57    CH.sub.3                                                                         CH.sub.3                                                                         2-[2-(5-BrC.sub.5 H.sub.3 N)CO]                                                           H   H                Z                                58    CH.sub.3                                                                         CH.sub.3                                                                         2-(3-CNC.sub.6 H.sub.4 CO)                                                                H   H                Z                                59    CH.sub.3                                                                         CH.sub.3                                                                         2-(3,5-F.sub.2 C.sub.6 H.sub.3 CO)                                                        H   H                Z                                60    CH.sub.3                                                                         CH.sub.3                                                                         2-(C.sub.6 H.sub.5 OCH.sub.2 CO)                                                          H   H                Z                                61    CH.sub.3                                                                         CH.sub.3                                                                         2-(4-FC.sub.6 H.sub.4 OCH.sub.2 CO)                                                       H   H                Z                                62    CH.sub.3                                                                         CH.sub.3                                                                         2-(3,5-di-CH.sub.3 OC.sub.6 H.sub.3 CO)                                                   H   H                Z                                63    CH.sub.3                                                                         CH.sub.3                                                                         2-(3-NO.sub.2 C.sub.6 H.sub.4 CO)                                                         H   H                Z                                64    CH.sub.3                                                                         CH.sub.3                                                                         2-(3-BrC.sub.6 H.sub.4 CO)                                                                H   H                Z                                65    CH.sub.3                                                                         CH.sub.3                                                                         2-(3-C.sub.2 H.sub.5 C.sub.6 H.sub.4 CO)                                                  H   H                Z                                66    CH.sub.3                                                                         CH.sub.3                                                                         2-(3,5-di-CH.sub.3 C.sub.6 H.sub.3 CO)                                                    H   H                Z                                67    CH.sub.3                                                                         CH.sub.3                                                                         2-(3-C.sub.2 H.sub.5 OC.sub.6 H.sub.4 CO)                                                 H   H                Z                                68    CH.sub.3                                                                         CH.sub.3                                                                         2-(3-FC.sub.6 H.sub.4 OCH.sub.2)                                                          H   H                Z                                69    CH.sub.3                                                                         CH.sub.3                                                                         2-(2,3-Cl.sub.2 C.sub.6 H.sub.3 CO)                                                       H   H                Z                                70    CH.sub.3                                                                         CH.sub.3                                                                         2-(2,3-F.sub.2 C.sub.6 H.sub.3 CO)                                                        H   H                Z                                71    CH.sub.3                                                                         CH.sub.3                                                                         2-(2-pyrimidyl-CO)                                                                        H   H                Z                                72    CH.sub.3                                                                         CH.sub.3                                                                         2-(4-pyrimidyl-CO)                                                                        H   H                Z                                73    CH.sub.3                                                                         CH.sub.3                                                                         2-di-CH.sub.3 NCO                                                                         H   H                Z                                __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________     ##STR10##                                                                    Compound                   Melting                                            No.   R.sup.1                                                                          R.sup.2                                                                          X          Y Z point (°C.)                                                                  olefinic*                                                                          isomer.sup.+                            __________________________________________________________________________    1     CH.sub.3                                                                         CH.sub.3                                                                         2-(3-ClC.sub.6 H.sub.4 CO)                                                               H H 80    7.75 Z                                       2     CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 CO                                                                     H H 93-5  7.61 Z                                       3     CH.sub.3                                                                         CH.sub.3                                                                         2-(4-FC.sub.6 H.sub.4 CO)                                                                H H            Z                                       4     CH.sub.3                                                                         CH.sub.3                                                                         2-(2-C.sub.4 H.sub.3 SCO)                                                                H H            Z                                       5     CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 OCO                                                                    H H            Z                                       6     CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.4 CH.sub.2 OCO                                                           H H            Z                                       7     CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.3 H.sub.7 OCO                                                                    H H            Z                                       8     CH.sub.3                                                                         CH.sub.3                                                                         2-( .sub.-- EC.sub.6 H.sub.5 CHCH)                                                       H H            Z                                       9     CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 CH.sub.2 CH.sub.2                                                      H H            Z                                       10    CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 CH.sub.2                                                               H H            Z                                       11    CH.sub.3                                                                         CH.sub.3                                                                         2-(2-C.sub.5 H.sub.4 NCO)                                                                H H            Z                                       12    CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 S                                                                      H H            Z                                       __________________________________________________________________________

                                      TABLE III                                   __________________________________________________________________________     ##STR11##                                                                    Compound                        Melting                                       No.   V R.sup.1                                                                          R.sup.2                                                                          X             Y Z point (°C.)                                                                  olefinic*                                                                          isomer.sup.+                       __________________________________________________________________________    1     O CH.sub.3                                                                         CH.sub.3                                                                         5-( .sub.-- E-4-ClC.sub.6 H.sub.4 CHCH)                                                     H H 138-9 7.62 Z                                  2     O CH.sub.3                                                                         CH.sub.3                                                                         5-( .sub.-- E-2,6-di-ClC.sub.6 H.sub.3 CHCH)                                                H H 119-121                                                                             7.75 Z                                  3     O CH.sub.3                                                                         CH.sub.3                                                                         5-( .sub.-- EC.sub.6 H.sub.5 CHCH)                                                          H H 138   7.76 Z                                  4     O CH.sub.3                                                                         CH.sub.3                                                                         5-C.sub.6 H.sub.5 CH.sub.2                                                                  H H            Z                                  5     O CH.sub.3                                                                         CH.sub.3                                                                         5-C.sub.6 H.sub.5 CO                                                                        H H            Z                                  6     O CH.sub.3                                                                         CH.sub.3                                                                         5-C.sub.6 H.sub.5 CH.sub.2 OCO                                                              H H            Z                                  __________________________________________________________________________

                                      TABLE IV                                    __________________________________________________________________________     ##STR12##                                                                    Compound                       Melting                                        No.   V R.sup.1                                                                          R.sup.2                                                                          X          Y Z   point (°C.)                                                                  olefinic*                                                                          isomer.sup.+                        __________________________________________________________________________     1    O CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 CO                                                                     H H   Oil   7.46 Z                                    2    O CH.sub.3                                                                         CH.sub.3                                                                         2-(2-ClC.sub.6 H.sub.4 CO)                                                               H H   159   7.57 Z                                    3    O CH.sub.3                                                                         CH.sub.3                                                                         2-.sup.n C.sub.4 H.sub.9                                                                 H H   Oil   7.64 Z                                    4    O CH.sub.3                                                                         CH.sub.3                                                                         2-(4-ClC.sub.6 H.sub.4 CO)                                                               H H   108-9 7.52 Z                                    5    O CH.sub.3                                                                         CH.sub.3                                                                         2-(4-FC.sub.6 H.sub.4 CO)                                                                H H    115-117                                                                            7.54 Z                                    6    O CH.sub.3                                                                         CH.sub.3                                                                         2-(4-CH.sub.3 C.sub.6 H.sub. 4 CO)                                                       H H   103-4 7.50 Z                                    7    O CH.sub.3                                                                         CH.sub.3                                                                         2-(3,5-Cl.sub.2 C.sub.6 H.sub.3 CO)                                                      H H   130-1 7.58 Z                                    8    O CH.sub.3                                                                         CH.sub.3                                                                         2-(2-C.sub.4 H.sub.3 SCO)                                                                H H    116-118                                                                            7.50 Z                                    9    O CH.sub.3                                                                         CH.sub.3                                                                         2-(4-C.sub.6 H.sub.5 C.sub.6 H.sub.4 CO)                                                 H H              Z                                   10    O CH.sub.3                                                                         CH.sub.3                                                                         2-CH.sub.3 OCO                                                                           H H              Z                                   11    O CH.sub.3                                                                         CH.sub.3                                                                         2-CN       H H              Z                                   12    O CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 CH.sub.2                                                               H H              Z                                   13    O CH.sub.3                                                                         CH.sub.3                                                                         2-( .sub.-- EC.sub.6 H.sub.5 CHCH)                                                       H H   Oil   7.44 Z                                   14    O CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 CH.sub.2 CH.sub.2                                                      H H              Z                                   15    O CH.sub.3                                                                         CH.sub.3                                                                         2-CH.sub.3 H H    81-2 7.65 Z                                   16    O CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 OCH.sub.2                                                              H H              Z                                   17    O CH.sub.3                                                                         CH.sub.3                                                                         2-CH.sub.3 H 5-NO.sub.2                                                                        Oil   7.61 Z                                   18    O CH.sub.3                                                                         CH.sub.3                                                                         2-(4-CH.sub.3 OC.sub.6 H.sub.4 CO)                                                       H H   140-5 7.52 Z                                   19    O CH.sub.3                                                                         CH.sub.3                                                                         2-(3-FC.sub.6 H.sub.4 CO)                                                                H H    76-7 7.54 Z                                   20    O CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 S                                                                      H H   100-1 7.50 Z                                   21    O CH.sub.3                                                                         CH.sub.3                                                                         2-(3-CH.sub.3 OC.sub.6 H.sub.4 CO)                                                       H H              Z                                   22    O CH.sub.3                                                                         CH.sub.3                                                                         2-(3-C.sub.4 H.sub.3 SCO)                                                                H H              Z                                   23    O CH.sub.3                                                                         CH.sub.3                                                                         2-(2-C.sub.4 H.sub.3 OCO)                                                                H H              Z                                   24    O CH.sub.3                                                                         CH.sub.3                                                                         2-(3-C.sub.4 H.sub.3 OCO)                                                                H H              Z                                   25    O CH.sub.3                                                                         CH.sub.3                                                                         2-(3-C.sub.5 H.sub.4 NCO)                                                                H H              Z                                   26    O CH.sub.3                                                                         CH.sub.3                                                                         2-(2-C.sub.5 H.sub.4 NCO)                                                                H H              Z                                   27    O CH.sub.3                                                                         CH.sub.3                                                                         3-(3-C.sub.2 H.sub.5 OC.sub.6 H.sub.4 CO)                                                H H              Z                                   28    O CH.sub.3                                                                         CH.sub.3                                                                         2-(3-CNC.sub.6 H.sub.4 CO)                                                               H H              Z                                   29    O CH.sub.3                                                                         CH.sub. 3                                                                        2-(3-ClC.sub.6 H.sub.4 CO)                                                               H H              Z                                   30    O CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 OCH.sub.2 CO                                                           H H              Z                                   31    O CH.sub.3                                                                         CH.sub.3                                                                         2-(4-FC.sub.6 H.sub.4 OCH.sub.2 CO)                                                      H H              Z                                   32    O CH.sub.3                                                                         CH.sub.3                                                                         2-(3,5-F.sub.2 C.sub.6 H.sub.3 CO)                                                       H H              Z                                   33    S CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.6 H.sub.5 CO                                                                     H H              Z                                   34    S CH.sub.3                                                                         CH.sub.3                                                                         2-(3-FC.sub.6 H.sub.4 CO)                                                                H H              Z                                   35    S CH.sub.3                                                                         CH.sub.3                                                                         2-(3-CH.sub.3 C.sub.6 H.sub.4 CO)                                                        H H              Z                                   36    S CH.sub.3                                                                         CH.sub.3                                                                         2-(3-CH.sub.3 OC.sub.6 H.sub.4 CO)                                                       H H              Z                                   __________________________________________________________________________

                                      TABLE V                                     __________________________________________________________________________     ##STR13##                                                                    Compound                Melting                                               No.   R.sup.1                                                                          R.sup.2                                                                          X         Y point (°C.)                                                                  olefinic*                                                                          isomer .sup.+                              __________________________________________________________________________    1     CH.sub.3                                                                         CH.sub.3                                                                         C.sub.6 H.sub.5                                                                         H Oil   7.63 Z                                          2     CH.sub.3                                                                         CH.sub.3                                                                         ( .sub.-- EC.sub.6 H.sub.5 CHCH)                                                        H 116-7 7.80 Z                                          3     CH.sub.3                                                                         CH.sub.3                                                                         C.sub.6 H.sub.5 CH.sub.2 CH.sub.2                                                       H 65-67 7.68 Z                                          4     CH.sub.3                                                                         CH.sub.3                                                                         C.sub.6 H.sub.5 CO                                                                      H            Z                                          5     CH.sub.3                                                                         CH.sub.3                                                                         4FC.sub.6 H.sub.4 CO                                                                    H            Z                                          6     CH.sub.3                                                                         CH.sub.3                                                                         CH.sub.3 OCO                                                                            H            Z                                          7     CH.sub.3                                                                         CH.sub.3                                                                         C.sub.6 H.sub.5 CH.sub.2                                                                H            Z                                          8     CH.sub.3                                                                         CH.sub.3                                                                         CN        H            Z                                          9     CH.sub.3                                                                         CH.sub.3                                                                         2-C.sub.4 H.sub.3 SCO                                                                   H            Z                                          __________________________________________________________________________     *Chemical shift of singlet from olefinic proton on betaalkoxyacrylate or      beta(alkylthio)-acrylate group.                                               (ppm from tetramethylsilane). Solvent: CDCl.sub.3                             .sup.+ Geometry of betaalkoxyacrylate or beta(alkylthio)acrylate group.       [C.sub.5 H.sub.4 N = pyridyl, C.sub.4 H.sub.3 S = thiophenyl, C.sub.4         H.sub.3 O = furyl, C.sub.5 H.sub.10 N = piperidinyl].                    

                  TABLE IA                                                        ______________________________________                                        NMR and Mass Spectral Data                                                    COM-                                                                          POUND                                                                         NO.                                                                           ______________________________________                                         1     3.76(3)s, 3.87(3)s, 6.28(1)m, 6.60(2)m, 6.76(2)q, 7.2-                        7.5(5)m, 7.71(1)s.                                                      2     3.72(3)s, 3.85(3)s, 6.31(1)m, 6.82(1)m, 6.90(1)m, 7.4-                        7.6(3)m, 7.49(1)s, 7.80(2)m. M.sup.+  285.                              3     3.78(3)s, 3.97(3)s, 6.28(1)q, 6.77(1)m, 6.88(1)m,                             7.67(1)s. M.sup.+  206.                                                 9     3.77(3)s, 3.92(3)s, 6.6-6.8(2)m, 7.26(1)m, 7.4-7.6(3)m,                       7.57(1)s, 7.8-7.9(2)m.                                                 10     3.76(3)s, 3.89(3)s, 6.30(1)m, 6.79(1)m, 6.96(1)m, 6.4-                        6.9(4)q, 7.55(1)s. M.sup.+  319.                                       11     2.16(3)s, 3.76(3)s, 3.87(3)s, 6.10(1)d, 6.78(1)d, 7.4-                        7.8(5)m, 7.58(1)s.                                                     12     3.72(3)s, 3.87(6)d, 6.3(1)m, 6.7-7.0(4)m, 7.46(1)s,                           7.8(2)m. M.sup.+  315.                                                 13     3.72(3)s, 3.86(3)s, 6.2(1)m, 6.5(1)m, 6.9(1)m, 7.2-                           7.4(3)m, 7.48(1)s.                                                     14     3.74(3), 3.87(3)s, 6.3(1)m, 6.6-7.2(4)m, 7.45(1)s,                            7.8(2)m. M.sup.+  303.                                                 15     3.70(3)s, 3.83(3)s, 6.2(1)m, 6.6(1)m, 6.8(1)m, 7.0-                           7.2(3)m, 7.2-7.6(1)m, 7.46(1)s. M.sup.+  303.                          16     1.35(9)s, 3.69(3)s, 3.52(3)s, 6.25(1)m, 6.8(1)m, 7.3-                         7.5(4)q, 7.46(1)s. M.sup.+  341                                        17     3.78(3)s, 3.93(3)s, 6.3(1)m, 6.8(1), 6.9(1)m, 7.55(1)s,                       7.8-8.0(4)q. M.sup.+  353.                                             18     3.60(3)s, 3.74(3)s, 6.40(1)m, 6.7(2)m, 6.9(2)m, 7.4(1)m                       7.53(1)s, 8.35(1)m. M.sup.+  290.                                      19     3.6(3) broad.s, 3.8(3) broad.s, 6.30(1)m, 6.6(1) broad.s                      6.70(1)m, 7.3(1)m, 7.5(1) broad.m, 7.9(1)m, 8.1(1)m,                          8.6(1)m.                                                               20     3.74(3)s, 3.78(3)s, 3.88(3)s, 6.28(1)m, 6.78(1)m,                             7.04(1)m, 7.50(1)s.                                                    21     1.37(9)s, 3.70(3)s, 3.82(3)s, 6.2(1)m, 6.7(1)m, 7.0(1)m,                      7.40(1)s. M.sup.+  265.                                                22     2.41(3)s, 3.71(3)s, 3.84(3)s, 6.28(1)m, 6.8(1)m,                              6.89(1)m, 7.21(2)d, 7.46(1)s, 7.72(2)d.                                23     3.72(3)s, 3.97(3)s, 6.22(1)q, 6.54(1)m, 6.89(1)m, 7.2-                        7.4(4)m, 7.46(1)s. M.sup.+  319.                                       24     3.72(3)s, 3.84(3)s, 6.33(1)m, 6.89(1)m, 7.0-7.2(2)                            7.47(1)s, 7.57(1)q, 7.77(1)q. M.sup.+  291.                            25     3.77(3)s, 3.93(3)s, 6.37(1)m, 6.87(1)m, 6.99(1)m, 7.5-                        7.6(2)m, 7.70(2)d. M.sup.+  353.                                       26     3.77(3)s, 3.92(3)s, 6.29(1)m, 6.58(1)m, 6.97(1)m,                             7.32(3)t, 7.57(1)s.                                                    ______________________________________                                        27     3.73(3)s, 3.87(3)s, 6.3(1)m, 6.7(1)m, 6.9(1)m, 7.1-                           7.6(4)m, 7.44(1)s. M.sup.+  303.                                       28     3.72(3)s, 3.85(3)s, 6.3(1)m, 6.8(1)m, 6.9(1)m, 7.2-                           7.8(4)m, 7.44(1)s. M.sup.+  319.                                       29     0.9(3)t, 1.6(2)m, 3.75(3)s, 3.88(3)s, 6.28(1)m, 6.77(1)m                      7.04(1)m, 7.50(1)s.                                                    30     1.47(9)s, 3.66(3)s, 3.80(3)s, 6.1(1)m, 6.5(1)m, 6.8(1)m,                      7.37(1)s. MH.sup.+  282.                                               34     3.74(3)s, 3.85(3)s, 6.38(1)m, 6.54(1)m, 6.91(1)m                              7.05(1)q, 7.47(1)q, 7.50(1)s, 7.62(1)q.                                40     2.40(3)s, 3.73(3)s, 3.87(3)s, 6.33(1)m, 6.85(1)m,                             6.94(1)m, 7.2-7.4(2)m, 7.51(1)s, 7.5-7.8(2)m.                          ______________________________________                                    

                  TABLE IIA                                                       ______________________________________                                        NMR and Mass Spectral Data                                                    COM-                                                                          POUND                                                                         NO.                                                                           ______________________________________                                        1       2.37(3)s, 3.76(3)s, 6.38(1)m, 6.87(1)m, 7.00(1)m, 7.3-                        7.9(5)m, 7.75(1)s.                                                    2       2.34(3)s, 3.69(3)s, 6.2(1)m, 6.7(1)m, 6.8(1)m, 7.2-                           7.8(5)m, 7.61(1)s. MH.sup.+  302.                                     ______________________________________                                    

                  TABLE IVA                                                       ______________________________________                                        NMR and Mass Spectral Data                                                    COM-                                                                          POUND                                                                         NO.                                                                           ______________________________________                                        1       3.70(3)s, 3.82(3)s, 7.04(1)s, 7.24(1)s, 7.4-7.6(3)m,                          7.46(1)s, 8.2-8.3(2)m. M.sup.+  286.                                  2       3.78(3)s, 3.94(3)s, 7.12(1)s, 7.25-7.5(3)m, 7.57(1)s,                         7.8(1)m. M.sup.+  320.                                                3       0.8-1.0(3)m, 1.1-1.8(4)m, 2.4-2.6(2)m, 3.76(3)s,                              3.94(3)s, 6.74(1)m, 7.02(1)m, 7.64(1)s.                               4       3.73(3)s, 3.88(3)s, 7.10(1)d, 7.31(1)d, 7.44(2)d,                             7.52(1)s, 8.30(2)d. M.sup.+  320.                                     5       3.74(3)s, 3.90(3)s, 7.0-7.4(4)m, 7.54(1)s, 8.42(2)q.                          M.sup.+  304.                                                         6       2.42(3)s, 3.71(3)s, 3.85(3)s, 7.18(1)d, 7.2-7.4(3)m,                          7.50(1)s, 8.22(2)d. M.sup.+  300.                                     7       3.78(3)s, 3.94(3)s, 7.17(1)d, 7.39(1)d, 7.58(1)s,                             7.59(1)t, 8.30(2)d. M.sup.+  354.                                     8       3.76(3)s, 3.90(3)s, 7.07(1)d, 7.17(1)q, 7.32(1)d,                             7.50(1)s, 7.70(1)q, 8.50(1)q. M.sup.+  292.                           13      3.67(3)s, 3.78(3)s, 6.16(1)d, 6.67(1)d, 6.85(1)d, 7.1-                        7.4(4)m, 7.44(1)s, 7.4-7.7(2)m. M.sup.+  284.                         15      2.25(3)s, 3.77(3)s, 3.95(3)s, 6.78(1)s, 7.02(1)s,                             7.65(1)s.                                                             17      2.28(3)s, 3.81(3)s, 4.02(3)s, 7.61(1)s, 7.73(1)s.                             M.sup.+  241.                                                         18      3.74(3)s, 3.89(3)s, 6.98(2)d, 7.09(1)d, 7.32(1)d                              7.52(1)s, 8.39(2)d. M.sup.+  316.                                     19      3.75(3)s, 3.91(3)s, 7.12(1)d, 7.1-7.6(2)m, 7.34(1)d,                          7.54(1)s, 7.9- 8.3(2)m. M.sup.+  304.                                 1       3.68(3)s, 3.84(3)s, 7.4-7.7(5)m, 7.63(1)s, 8.08(1)s.                          M.sup.+  259.                                                         2       3.77(3)s, 3.96(3)s, 6.68(1)d, 7.3-7.6(5)m, 7.77(1)d,                          7.80(1)s, 8.04(1)s. MH.sup.+  285.                                    3       2.7-3.2(4)m, 3.76(3)s, 3.95(3)s, 7.1-7.4(5)m, 7.68(1)s,                       7.98(1)s. M.sup.+  287.                                               ______________________________________                                         key:                                                                          pp from tetramethylsilane; (integral),s--singlet, d--doublet, t--triplet,     q--quartet, m--multiplet.                                                     M.sup.+ --Mass spectrum molecular ion.                                   

The compounds of the invention having the general formula (I) can beprepared from substituted heterocyclic compounds of general formula (II)by the steps shown in Scheme I.

Throughout Scheme I the terms A, B, E, D, R¹ and R² are as definedabove, and L is a leaving group such as a halogen (iodine, bromine orchlorine) atom. ##STR14##

Compounds of general formula (IV) can be prepared by treatment ofsubstituted acetic esters of general formula (III) with a base and aformic ester such as methyl formate or HCO₂ R¹ wherein R¹ is as definedabove, in a suitable solvent. If the reaction is quenched with asuitable species of general formula R² L or R₂ ² SO₄ wherein R² is asdefined above but is not hydrogen and L is a leaving group such as ahalogen atom, compounds of general formula (I) may be obtained.

Alternatively, compounds of general formula (IV) may be isolated byquenching the reaction with water or an acid. In such cases, conversioninto compounds of general formula (I) is performed in a separate step bytreatment with a suitable base (such as sodium carbonate or potassiumcarbonate) and a suitable reagent of general formula R² L or R₂ ² SO₄,wherein R² and L are as defined above, in a suitable solvent.

Alternatively, alkali metal salts of compounds of general formula (IV)may be isolated and converted into compounds of general formula (I) bytreatment with a suitable reagent of general formula R₂ L or R₂ ² SO₄,wherein R² and L are as defined above in a suitable solvent, as asubsequent step.

Compounds of general formula (III) can be prepared by treatment ofheterocyclic compounds of general formula (II) with a suitable base suchas sodium hydride and a substituted acetic ester of general formula LCH₂CO₂ R¹ wherein R¹ and L are as defined above, in a suitable solvent.

Compounds of general formula (I) in which --OR² -- is a group --SR²where S is sulphur may be obtained by treating compounds of generalformula (IV) with a suitable reagent of general formula R² SO₂ Clwherein R² is defined above, in a suitable solvent and then quenchingwith a reagent of general formula NaSR² e.g. sodium methanethiolate.

Compounds of general formula (II) can be prepared by standard methodsdescribed in the chemical literature. For example, heterocycliccompounds of general formula (II), in which each of A, B and D is thegroup ═CH-- and E is the group ═CZ-- wherein Z is (E)--Aryl--CH═CH, maybe prepared via the Wittig reaction between the appropriate phosphoraneand the 2- formylpyrrole (see, for example, R A Jones, T Pojarlieva andR J Heal, Tetrahedron, 1968, 24, 2013, and references therein).

Compounds of general formula (II) in which each of A, B and D is thegroup ═CH-- and E is the group ═CZ-- wherein Z is ArylCO--, may beprepared via the Vilsmeier-Haack reaction of the appropriate benzamideand the appropriate pyrrole in phosphoryl chloride (see, for example, GMcGillivray and J White, J.Org.Chem. 1977, 42, 4248, and referencestherein).

Compounds of general formula (II) in which both B and D are the group═CH--, A is the group ═N--, and E is the group ═CZ-- wherein Z isArylCO--, may be prepared by the reaction of the appropriatebenzoylchloride and imidazole in a suitable base (see, for example, L.A. M. Bastiaansen and E. F. Godefroi, Synthesis, 1982, 675, andreferences therein).

Compounds of general formula (III) in which each of A, B and D is thegroup ═CH-- and E is the group ═CZ-- wherein Z is defined above, may beprepared from the reaction of the appropriate2,5-dimethoxytetrahydrofuran and the appropriate esters of glycine in asuitable solvent such as acetic acid (see, for example, C W Jefford andW Johncock, Helv Chim Acta, 1983, 2661, and references therein).

Compounds of general formula (III) in which B is the group ═CH-- andeach of A and D is the group ═N-- and E is the group ═CZ-- wherein Z isAryl may be prepared by the reaction of the appropriate acylamidine andthe appropriately substituted hydrazine in a suitable solvent such asacetic acid to form a triazole ring (see, for example, Yang-i Lin etal., J.Org.Chem. , 1979, 44, 4160, and references therein).

The compounds of formula I and compositions containing them, arevariously active against a wide range of fungal diseases, particularly,for example, against

Pyricularia oryzae on rice

Puccinia recondita, Puccinia striformis and other rusts on wheat,Puccinia hordei, Puccinia striiformis and other rusts on barley, andrusts on other hosts e.g. coffee, pears, apples, vegetables andornamental plants Erysiphe graminis (powdery mildew) on barley and wheatand other powdery mildews on various hosts such as Spaerotheca macularison hops.

Sphaerotheca fuliginea on cucurbits (e.g. cucumber) Podosphaeraleucotricha on apples and Uncinula necator on vines Helminthosporiumspp., Rhynchosporium spp. and Pseudocercosporellaherpotrichoides oncereals Cercospora arachidicola and Cercosporidum personata on peanutsand other Cercospora species on for example sugar beet, bananas and soyabeans and rice. Botrytis cinerea (grey mould) on tomatoes, strawberries,vegetables, vines and other hosts Alternaria species on vegetables (e.g.cucumber, oil-seed rape, apples, tomatoes and other hosts). Venturiainaequalis (scab) on apples and Plasmopara viticola (downy mildew) onvines.

Other downy mildews such as Bremia lactucae on lettuce, Peronospora spp.on soybeans, tobacco, onions and other hosts and Pseudoperonosporahumuli on hops and Pseudoperonospora cubensis on cucurbits Phytophthorainfestans on potatoes and tomatoes and other Phytophthora spp. onvegetables, strawberries, avocado, pepper, ornamentals, tobacco, cocoaand other hosts. Thanatephorus cucumeris on rice and other Rhhizoctoniaspecies on various hosts such as wheat and barley, vegetables, cottonand turf.

Some of the compounds have also shown a broad range of activitiesagainst fungi in vitro. They have activity against various post-harvestdiseases of fruit (e.g. Penicillium digitatum and italicum andTrichoderma viride on oranges and Gloesporium musarum on bananas).

Further some of the compounds are active as seed dressings againstFusarium spp., Septoria spp., Tilletia spp. (bunt, a seed borne diseaseof wheat), Ustilago spp., Helminthosporium spp. on cereals, Rhizoctoniasolani on cotton and Pyricularia oryzae on rice.

The compounds can move acropetally in the plant tissue. Moreover, thecompounds can be volatile enough to be active in the vapour phaseagainst fungi on the plant.

The compounds may also be useful as industrial (as opposed toagricultural ) fungicides, e.g. in the prevention of fungal attack onwood, hides, leather and especially paint films.

This invention, therefore, includes the foregoing uses of the compounds(and compositions containing them) in addition to their principal use asplant fungicides.

The compounds may be used as such for fungicidal purposes but are moreconveniently formulated into compositions for such usage. The inventionthus provides a fungicidal or plant growth regulating compositioncomprising a compound of general formula (I) as hereinbefore defined,and, optionally, a carrier or diluent.

The invention also provides a method of combating fungi, which comprisesapplying to a plant, to seed of a plant, or to the locus of the plant orseed, a compounds as hereinbefore defined, or a composition containingthe same.

The compounds, can be applied in a number of ways. For example they canbe applied, formulated or unformulated, directly to the foliage of aplant, to seeds or to other medium in which plants are growing or are tobe planted. They can be sprayed on, dusted on or applied as a cream orpaste formulation, or they can be applied as a vapour or as slow releasegranules. Application can be to any part of the plant including thefoliage, stems, branches or roots, or to soil surrounding the roots, orto the seed before it is planted; or to the soil generally, to paddywater or to hydroponic culture systems. The invention compounds may alsobe injected into plants or sprayed onto vegetation using electrodynamicspraying techniques or other low volume methods.

The term "plant" as used herein includes seedlings, bushes and trees.Furthermore, the fungicidal methods of the invention includespreventative, protectant, prophylactic and eradicant treatment.

The compounds are preferably used for agricultural and horticulturalpurposes in the form of a composition. The type of composition used inany instance will depend upon the particular purpose envisaged.

The compositions may be in the form of dustable powders or granulescomprising the active ingredient (invention compound) and a soliddiluent or carrier, for example fillers such as kaolin, bentonits,kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia,Fuller's earth, gypsum, diatomaceous earth and China clay. Such granulescan be preformed granules suitable for application to the soil withoutfurther treatment. These granules can be made either by impregnatingpellets of filler with the active ingredient or by pelleting a mixtureof the active ingredient and powdered filler. Compositions for dressingseed may include an agent (for example a mineral oil) for assisting theadhesion of the composition to the seed; alternatively the activeingredient can be formulated for seed dressing purposes using an organicsolvent (for example N-methylpyrrolidone, propylene glycol ordimethylformamide). The compositions may also be in the form of wettablepowders or water dispersible granules comprising wetting or dispersingagents to facilitate their dispersion in liquids. The powders andgranules may also contain fillers and suspending agents.

Emulsifiable concentrates or emulsions may be prepared by dissolving theactive ingredient in an organic solvent optionally containing a wettingor emulsifying agent and then adding the mixture to water which may alsocontain a wetting or emulsifying agent. Suitable organic solvents arearomatic solvents such as alkylbenzenes and alkylnaphthalenes, ketonessuch as isophorone, cyclohexanone and methylcyclohexanone, chlorinatedhydrocarbons such as chlorobenzene and trichlorethane, and alcohols suchas furfuryl alcohol, butanol and glycol ethers.

Suspension concentrates of largely insoluble solids may be prepared byball or bead milling with a dispersing agent and including a suspendingagent to stop the particles of the solid settling.

Compositions to be used as sprays may be in the form of aerosols whereinthe formulation is held in a container under pressure in the presence ofa propellant, e.g. fluorotrichloromethane or dichlorodifluoromethane.

The invention compounds can be mixed in the dry state with a pyrotechnicmixture to form a composition suitable for generating in enclosed spacesa smoke containing the compounds.

Alternatively, the compounds may be used in micro-encapsulated form.They may also be formulated in biodegradable polymeric formulations toobtain a slow, controlled release of the active substance.

By including suitable additives, for example additives for improving thedistribution, adhesive power and resistance to rain on treated surfaces,the different compositions can be better adapted for various utilities.

The invention compounds can be used as mixtures with fertilisers (e.g.nitrogen-, potassium- or phosphorus-containing fertilisers).Compositions comprising only granules of fertiliser incorporating, forexample coated with, the compound are preferred. Such granules suitablycontain up to 25% by weight of the compound. The invention thereforealso provides a fertiliser composition comprising a fertiliser and thecompound of general formula (I) or a salt or metal complex thereof.

Wettable powders, emulsifiable concentrates and suspension concentrateswill normally contain surfactants e.g. a wetting agent, dispersingagent, emulsifying agent or suspending agent. These agents can becationic, anionic or non-ionic agents.

Suitable cationic agents are quaternary ammonium compounds, for examplecetyltrimethylammonium bromide. Suitable anionic agents are soaps, saltsof aliphatic monoesters of sulphuric acid (for example sodium laurylsulphate), and salts of sulphonated aromatic compounds (for examplesodium dodecylbenzenesulphonate, sodium, calcium or ammoniumlignosulphonate, butylnaphthalene sulphonate, and a mixture of sodiumdiisopropyl- and triisopropyl-naphthalene sulphonates).

Suitable non-ionic agents are the condensation products of ethyleneoxide with fatty alcohols such as olely or cetyl alcohol, or with alkylphenols such as octyl- or nonyl-phenol and octylcresol. Other non-ionicagents are the partial esters derived from long chain fatty acids andhexitol anhydrides, the condensation products of the said partial esterswith ethylene oxide, and the lecithins. Suitable suspending-agents arehydrophilic colloids (for example polyvinylpyrrolidone and sodiumcarboxymethylcellulose), and swelling clays such as bentonits orattapulgite.

Compositions for use as aqueous dispersions or emulsions are generallysupplied in the form of a concentrate containing a high proportion ofthe active ingredient, the concentrate being diluted with water beforeuse. These concentrates should preferably be able to withstand storagefor prolonged periods and after such storage be capable of dilution withwater in order to form aqueous preparations which remain homogeneous fora sufficient time to enable them to be applied by conventional sprayequipment. The concentrates may conveniently contain up to 95%, suitably10-85%, for example 25-60%, by weight of the active ingredient. Afterdilution to form aqueous preparations, such preparations may containvarying amounts of the active ingredient depending upon the intendedpurpose, but an aqueous preparation containing 0.0005% or 0.01% to 10%by weight of active ingredient may be used.

The compositions of this invention may contain other compounds havingbiological activity, e.g. compounds having a similar or complementaryfungicidal activity or plant posses plant growth regulating, herbicidalor insecticidal activity.

A fungicidal compound which may be present in the composition of theinvention may be one which is capable of combating ear disease ofcereals (e.g. wheat) such as Septoria, Gibberella and Helminthosporiumspp., seed and soil borne diseases and downy and powdery mildews ongrapes and powdery mildew and scab on apple etc. By including anotherfungicide, the composition can have a broader spectrum of activity thanthe compound of general formula (I) alone. Further to the otherfungicide can have a synergistic effect on the fungicidal activity ofthe compound of general formula (I). Examples of fungicidal compoundswhich may be included in the composition of the invention arecarbendazim, benomyl, thiphanate-methyl, thiabendazole, fuberidazole,etridazole, dichlorofluanid, cymoxanil, oxadixyl, ofurace, metalaxyl,furalaxyl, benalaxyl, fosetyl aluminjure, fenarimol, iprodione,procymidone, vinclozolin, penconazole, myclobutanil, R0151297, S3308,pyrazophos, ethirimol, ditalimfos, tridemorph, triforine, nuarimol,triazbutyl, guazatine, propiconazole, prochloraz, flutriafol,chlortriafol i.e. the chemical 1-(1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-hexan-2-ol, DPXH6573(1-((bis-4-fluorophenyl)methylsilyl)-methyl)-1H-1,2,4-triazole,triadimefon, triadimenol, diclobutrazol, fenpropimorph, fenpropidine,chlorozolinate, diniconazol, imazalil, fenfuram, carboxin, oxycarboxln,methfuroxam, dodemorph, BAS 454, blasticidin S, kasugamycin, edifenphos,kitazin P, cycloheximide, phthalide, probenazole, isoprothiolane,tricyclazole, pyroquilan, chlorbenzthiazone, neoasozin, polyoxin D,validamycin A, repronil, flutolanil, pencycuron, diclomezine, phenazinoxide, nickel dimethyldithiocarbamate, techlofthalam, bitertanol,bupirimate, etaconazole, streptomycin, cypofuram, biloxazol,quinomethionate, dimethirimol, 1-(2-cyano-2-methoxyimino-acetyl)-3-ethyl urea, fenapanil,tolclofosmethyl, pyroxyfur, polyram, maneb, mancozeb, captafol,chlorothalonil, anilazine, thiram, captan, folpet, zineb, propineb,sulphur, dinocap, binapactryl, nitrothalisopropyl, dodine, dithianon,fentin hydroxide, fentin acetate, tecnazene, quintozene, dichloran,copper containing compounds such as copper oxychloride, copper sulphateand Bordeaux mixture, and organomercury compounds.

The compounds of general formula (I) can be mixed with soil, peat orother rooting media for the protection of plants against seed-borne,soil-borne or foliar fungal diseases.

Suitable insecticides which may be incorporated in the composition ofthe invention include pirimicarb, dimethoate, demeton-s-methyl,formothion, carbaryl, isoprocarb, XMC, BPMC, carbofuran, carbosulfan,diazinon, fenthion, fenitrothion, phenthoate, chlorpyrifos, isoxathion,propaphos, momocrotophas, buprofezin, ethroproxyfen and cycloprothrin.

Plant growth regulating compounds are compounds which control weeds orseedhead formation, or selectively control the growth of less desirableplants (e.g. grasses).

Examples of suitable plant growth regulating compounds for use with theinvention compounds are the gibberellins (e.g. GA₃, GA₄ or GA₇) , theauxins (e.g. indoleacetic acid, indolebutyric acid, naphthoxyacetic acidor naphthylacetic acid), the cytokinins (e.g. kinetin, diphenylurea,benzimidazole, benzyladenine or benzylaminopurine), phenoxyacetic acids(e.g. 2,4-D or MCPA), substituted benzoic acids (e.g. triiodobenzoicacid) , morphactins (e.g. chlorfluoroecol), maleic hydrazide,glyphosate, glyphosine, long chain fatty alcohols and acids, dikegulac,paclobutrazol, flurprimidol, fluoridamid, mefluidide, substitutedquaternary ammonium and phosphonium compounds (e.g. chloromequatchlorphonium or mepiquatchloride), ethephon, carbetamide,methyl-3,6-dichloroanisate, daminozide, asulam, abscisic acid,isopyrimil,1-(4-chlorophenyl)-4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylicacid, hydroxybenzonitriles (e.g. bromoxynil) , difenzoquat,benzoylprop-ethyl 3,6-dichloropicolinic acid, fenpentezol, inabenfide,triapenthenol and tecnazene.

The following Examples illustrates the invention. Throughout theseexamples, magnesium sulphate was used to dry solutions, and reactionsinvolving water-sensitive intermediates were performed under anatmosphere of nitrogen.

EXAMPLE 1

This Example illustrates the preparation of (Z)-methyl3-methoxy-2-[(E)-2-styrylpyrrol-1-yl]acrylate (Compound No. 1 of TableI).

Sodium hydride (2.4 g, 0.05 mol of 50% dispersion in oil) was washedwith petrol 40°-60° and suspended in dry tetrahydrofuran, (THF 50 ml).Pyrrole-2-carboxaldehyde (4.75 g, 0.05 mol) in THF (25 ml) was addeddropwise over 1 hour at room temperature. After a further 11/2 hoursbenzyltriphenylphoephoniuxn chloride (19.5 g, 0.05 mol) was addedportionwise (solution becomes red, exotherm) and it was stirred for 3hours at 50° C. The mixture was concentrated under reduced pressure,water was added to the residue and it was extracted with diethyl ether.After drying with magnesium sulphate and evaporation a viscous red oilresulted. Purification by column chromatography using silica gel withpetroleum ether 60°-80°: diethyl ether (1:1) as the eluent gave a waxysolid (5.3 g). This was recrystallised from petrol 60°-80°: chloroformto give (M)-2-styrylpyrrole (1.5 g) as a crystalline solid which isunstable to light.

Sodium hydride (0.3 g, 0.0063 mol) was washed with petrol 60°-80° andsuspended in dimethylformamide (DMF, 25 ml). The (E)-2-styrylpyrrole(1.0 g, 0.006 mol) in DMF (10 ml) was added dropwise at roomtemperature. After stirring for 11/2 hours, methyl bromoacetate (0.56ml, 0.006 mol) in DMF (5 ml) was added dropwise. After 16 hours it waspoured into water (200 ml) and extracted with ether (3×100 ml). Theextracts were washed with brine dried and evaporated under reducedpressure to give a brown oil. Purification by column chromatographyusing silica gel with ethyl acetate: petrol 60°-80°, (1:1) as the eluentgave methyl (2-styrylpyrrol-1-yl)acetate (0.5 g, 30% yield) as a buffamorphous solid.

Sodium hydride (0.63 g, 0.013 mol) was washed with petrol 60°-80° andsuspended in DMF (30 ml) under nitrogen. To this methyl(2-styrylpyrrol-1-yl)acetate (1.6 g, 0.0066 mol) and methyl formate (8.2ml, 0.13 mol) in DMF (10 ml) was added dropwise at room temperature.After 4 hours it was poured into 200 ml of saturated sodium bicarbonate,extracted with diethyl ether (2×100 ml), then the aqueous layer wasneutralised with concentrated hydrochloric acid and extracted again withdiethyl ether (2'100 ml). This was washed with brine, dried andevaporated to give methyl 3-hydroxy-2-[(E)-2-styrylpyrrol-1-yl]acrylate(2.0 g) as an orange-yellow oil. This was used in the following reactionwithout further purification.

To a stirred suspension of potassium carbonate (1.8 g, 0.013 mol) in DMF(50 ml) the methyl 3-hydroxy-2-[(E)-2-styrylpyrrol-1-yl]acrylate (2.0 g,0.0074 mol) in DMF (20 ml) was added dropwise. After stirring for 2hours at room temperature, dimethyl sulphate (0.63 ml, 0.0067 mol) wasadded dropwise (slight exotherm). This was stirred for 16 hours thenpoured into saturated sodium bicarbonate solution (200 ml) and extractedwith diethyl ether (2×100 ml). The extracts were washed with brine,dried and evaporated under reduced pressure to give a viscous orangeoil. Purification by column chromatography using silica gel with diethylether: petrol 60°-80°, (1:1) as the eluent gave the tile compound (700mg, 37% yield) as a pale yellow solid melting at 126°-8° C.

EXAMPLE 2

This Example illustrates the preparation of (Z)methyl3-methoxy-2-[2-benzoylpyrrol-1-yl ]acrylate (Compound No. 2 of Table I).

Potassium tert-butoxide (7.22, 0.064 mol) was dissolved in DMF (40 ml)and 2-benzoylpyrrole (10 g, 0.058 mol) in DMF (10 ml) was added dropwisewith stirring at room temperature. This was left for 16 hours thencooled to 0° C. when methyl bromoacetate (5.4 ml, 0.058 mol) in DMF (5ml) was added dropwise. The reaction mixture was stirred for 16 hoursthen poured into water (150 ml) and extracted with diethyl ether (2×100ml). The extracts were washed with brine (2×75 ml) dried and evaporatedto give methyl (2-benzoylpyrrol-1-yl)acetate (12.6 g, 89%) as a brownoil which crystallised on standing.

Sodium hydride (1.44 g, 55% in oil, 0.033 mol) was washed with petrol60°-80° and suspended in DMF (15 ml). To this the methyl(2-benzoylpyrrol-1-yl)acetate (4.0 g, 0.0165 mol) in DMF (15 ml) andmethyl formate (20.3 ml, 0.33 mol) was added dropwise at roomtemperature. After 4 hours it was poured into 200 ml of 10% potassiumcarbonate, washed with diethyl ether (2×100 mls), then the aqueous wasneutralised with concentrated hydrochloric acid and extracted withdiethyl ether (2×100 ml). These extracts were washed with brine, driedand evaporated to give methyl 3-hydroxy-2-(2-benzoylpyrrol-1-yl)acrylate (3.86 g, 86%) as a white crystallinesolid melting at 112°-113°.

To a stirred suspension of potassium carbonate (5.0 g, 0.037 mol) in DMF(50 ml) the methyl 3-hydroxy-2-(2-benzoyl-pyrrol-1-yl)acrylate (5.0 g,0.0185 mol) in DMF (10 ml) was added dropwise. After stirring for 2hours at room temperature, dimethyl sulphate (1.75 ml, 0.0185 mol) wasadded dropwise (slight exotherm). This was stirred for 3 hours thenpoured into saturated sodium bicarbonate solution (200 ml) and extractedwith diethyl ether (2×100 ml). The extracts were washed with brine,dried and evaporated under reduced pressure to give a viscous orangeoil. Purification by column chromatography using silica gel with ethylacetate as the eluent gave the title compound (3.7 g, 70%) a whitecrystalline solid melting at 78°-79° C. See Table IA for NMR and massspectral data.

EXAMPLE 3

This Example illustrates the preparation of (Z)-methyl3-methylthio-2-[2-(3-chlorobenzoyl)pyrrol-1-yl]-acrylate (Compound No. 1of Table II).

To a solution of methyl3-hydroxy-2-[2-(3-chlorobenzoyl)pyrrol-1-yl]acrylate (2.14 g, 0.007 mol,obtained using the same procedure as Example 2) in triethylamine (1.1ml, 0.008 mol) and dichloromethane (40 ml) at 0° C., methanesulphonylchloride (0.6 ml, 0.077 mol) was added dropwise at 0° C. After 2 hours,sodium methanethiolate (0.5 g, 0.0071 mol) was added and the mixturestirred for 16 hours. This was poured into aqueous sodium hydroxidesolution (75 ml, 10%), the organic phase was separated and washed withwater then dried and evaporated under reduced pressure to give a brownoil. Purification by medium pressure column chromatography using silicagel with diethyl ether as the eluant gave the title compound (1.4 g,60%) as a buff crystalline solid melting at 80° C. See Table IIA for NMRdata.

EXAMPLE 4

This Example illustrates the preparation of (Z)-methyl3-methoxy-2-[5-phenyl-1,2,4-triazol-1-yl]acrylate (Compound No. 1 ofTable V).

N-[(Dimethylamino)methylene]benzamide (2.0 g, 0.011 mol) and methylhydrazine acetate hydrochloride salt (1.9 g, 0.011 mol) were warmed inacetic acid at 90° C. for 11/2 hours. The acetic acid was evaporatedunder reduced pressure and the residue neutralised with saturatedaqueous sodium bicarbonate, then extracted into chloroform (2×100 ml)washed with water, dried and evaporated under reduced pressure to givemethyl [5-phenyl-1,2,4-triazol-1-yl]acetate as a clear oil (2.3 g, 96%).

Sodium hydride (0.88 g, 0.018 mol, 50% dispersion in oil) was washedwith dry petrol 40°-60° and suspended in DMF (15 ml). A mixture ofmethyl [5-phenyl-1,2,4-triazol-1-yl]-acetate (2.0 g, 0.009 mol) andmethyl formate (11.4 ml, 0.18 mol) in DMF (15 ml) was added at roomtemperature with stirring over 10 minutes. After 2 hours aqueouspotassium carbonate (200 ml, 10%) was added and the aqueous layerextracted with diethyl ether (2×100 ml), then the aqueous layer wasneutralised with concentrated hydrochloric acid and then extracted withethyl acetate (3×150 ml). The ethyl acetate extract was washed withbrine and dried then evaporated under reduced pressure to give methyl3-hydroxy-2-[5-phenyl-1,2,4-triazol-1-yl acrylate (2.2 g) as a yellowoil.

To a stirred suspension of potassium carbonate (2.6 g, 0.018 mol) in DMF(25 ml) the methyl 3-hydroxy-2-[5- phenyl-1,2,4-triazol-1-yl]acrylate(2.2 g, 0.009 mol) in DMF (10 ml) was added dropwise. After stirring for11/2 hours at room temperature, dimethyl sulphate (0.87 ml, 0.009 mol)was added (slight exotherm). This was stirred for 3 hours then pouredinto water (150 ml) and extracted with ethyl acetate (3×75 ml). Theextracts were washed with brine, dried and evaporated under reducedpressure to give a clear oil. Purification by column chromatographyusing silica gel with ethyl acetate as the eluant gave the titlecompound (1.5 g, 64%) as a clear oil. See Table VA for NMR and massspectrum data.

EXAMPLE 5

This Example illustrates the preparation of (Z)-methyl3-methoxy-2 -(pyrrol-1-yl)acrylate (Compound No. 55 of Table I).

A solution of the hydrochloride salt of the methyl ester of glycine(6.30 g) and potassium acetate (8.00 g) in water (10 ml) was added toglacial acetic acid (50 ml). The resulting mixture was heated to reflux,2,5-dimethoxytetrahydrofuran (6.60 g) was added in one portion, andheating under reflux was continued for 4 hours. After cooling, thereaction mixture was neutralised with sodium bicarbonate and extractedwith ethyl acetate. The extracts were washed with water, dried,concentrated under reduced pressure, and distilled at 125° C. and ca. 15torr using a short-path distillation apparatus to give methylpyrrol-1-ylacetate (2.62 g, 38% yield) as a colourless liquid, infra red(film) 1750 cm⁻¹.

A solution of methyl pyrrol-1-ylacetate (2.00 g) in methyl formate (4.4ml) was added dropwise to a stirred suspension of sodium hydride (0.38g) in dry toluene (10 ml) cooled in an ice bath. The mixture was allowedto warm to room temperature, 2 drops of dry methanol were added(effervescence), and it was heated slowly to 50° C. whereupon themixture became at first clear, then deposited a thick off-white solid.The mixture was heated at 50° C. for 30 minutes, allowed to cool anddiluted with ether. The solid was filtered off, washed with ether andpartially dried to give a white solid (3.12 g) , infrared (film) 1665,1650 cm⁻¹. Methyl iodide (0.93 ml) was added in one portion to a stirredsuspension of this solid in DMF (20 ml). After stirring at roomtemperature for 2 hours, the mixture was poured into water and extractedwith ether. The extracts were washed with water, dried and concentratedto give a white solid (2.35 g) which was triturated with petrol anddried to give the title compound (1.73 g, 66% yield) as a white solid,melting point 88°-89° C., infrared (nujol mull) 1700, 1635 cm⁻¹, protonnmr (CDCl₃) delta: 3.77 (3H,singlet); 3.91 (3H, singlet); 6.26(2H,triplet J 5 Hz), 6.69 (2H,triplet J 5 Hz); 7.51 (1H, singlet) ppm.NOTE : On treatment with trichloroacetyl chloride and2,6-dimethylpyridine in refluxing chloroform, and then, in a subsequentstep, with potassium carbonate in propan-1-ol, the title compound wasconverted into (Z)-methyl3-methoxy-2-[(2-prop-1-yloxycarbonyl)pyrrol-1-yl ]acrylate, compound No.29 of Table I.

EXAMPLE 6

An emulsifiable concentrate is made up by mixing the ingredients, andstirring the mixture until all the constituents are dissolved.

    ______________________________________                                        Compound No 2 of Table I                                                                             10%                                                    Isophorone             25%                                                    Calcium dodecylbenzenesulphonate                                                                      5%                                                    Nonylphenolethoxylate (13 moles                                                                      10%                                                    ethylene oxide)                                                               Alkyl benzenes         50%                                                    ______________________________________                                    

EXAMPLE 7

The active ingredient is dissolved in methylene dichloride and theresultant liquid sprayed onto the granules of attapulgite clay. Thesolvent is then allowed to evaporate to produce a granular composition.

    ______________________________________                                        Compound No 11 of Table I                                                                              5%                                                   Attapulgite granules     95%                                                  ______________________________________                                    

EXAMPLE 8

A composition suitable for use as a seed dressing is prepared bygrinding and mixing the three ingredients.

    ______________________________________                                        Compound No 14 of Table I                                                                              50%                                                  Mineral oil              2%                                                   China clay               48%                                                  ______________________________________                                    

EXAMPLE 9

A dustable powder is prepared by grinding and mixing the activeingredient with talc.

    ______________________________________                                        Compound No 14 of Table I                                                                              5%                                                   Talc                     95%                                                  ______________________________________                                    

EXAMPLE 10

A suspension concentrate is prepared for chemicals which are largelyinsoluble solids by ball milling, for example, the constituents set outbelow, to form an aqueous suspension of the ground mixture with water.

    ______________________________________                                        Compound No 2 of Table I 40%                                                  Sodium lignosulphonate   10%                                                  Bentonite clay           1%                                                   Water                    49%                                                  ______________________________________                                    

This formulation can be used as a spray by diluting into water orapplied directly to seed.

EXAMPLE 11

A wettable powder formulation is made by mixing together the ingredientsset out below and then grinding the mixture until all are thoroughlymixed.

    ______________________________________                                        Compound No 11 of Table I                                                                              25%                                                  Sodium lauryl sulphate   2%                                                   Sodium lignosulphonate   5%                                                   Silica                   25%                                                  China clay               43%                                                  ______________________________________                                    

EXAMPLE 12

A Col formulation was prepared by ball-milling the constituents set outbelow and then forming an aqueous suspension of the ground mixture withwater.

    ______________________________________                                        Compound No 14 of Table I                                                                              40%                                                  "Dispersol" T            10%                                                  "Lubrol" APN5            1%                                                   Water                                                                         ______________________________________                                    

EXAMPLE 13

A dispersible powder formulation was made by mixing together theingredients set out below and then grinding the mixture until all werethoroughly mixed.

    ______________________________________                                        Compound No 11 of Table I                                                                              25%                                                  "Aerosol" OT/B           2%                                                   "Dispersol" A.C.         5%                                                   China clay               28%                                                  Silica                   40%                                                  ______________________________________                                    

In Examples 6 to 13 the proportions of the ingredients given are byweight. The remaining compounds of Tables I, II, III, IV and V were allsimilarly formulated as for Examples 6 to 13.

There now follows an explanation of the compositions or substancesrepresented by the various Trade Marks and Trade Names mentioned above.

DISPERSOL T & AC : a mixture of sodium sulphate and a condensate offormaldehyde with sodium naphthalene sulphonate

LUBROL APN5 : a condensate of nonyl phenol (1 mole) with naphthaleneoxide (5.5 moles)

AEROSOL OT/B : dioctyl alkyl naphthalene sulphonate

EXAMPLE 14

The compounds were tested against a variety of foliar fungal diseases ofplants. The technique employed was as follows.

The plants were grown in John Innes Potting Compost (No 1 or 2) in 4 cmdiameter minipots. The test compounds were formulated either by beadmilling with aqueous Dispersol T or as a solution in acetone oracetone/ethanol which was diluted to the required concentrationimmediately before use. For the foliage diseases, the formulations (100ppm active ingredient) were sprayed on to the foliage and applied to theroots of the plants in the soil. The sprays were applied to maximumretention and the root drenches to a final concentration equivalent toapproximately 40 ppm a.i./dry soil. Tween 20, to give a finalconcentration of 0.05%, was added when the sprays were applied tocereals.

For most of the tests the compound was applied to the soil (roots) andto the foliage (by spraying) one or two days before the plant wasinoculated with the disease. An exception was the test on Erysiphegraminis in which the plants were inoculated 24 hours before treatment.Foliar pathogens were applied by spray as spore suspensions onto theleaves of test plants. After inoculation, the plants were put into anappropriate environment to allow infection to proceed and then incubateduntil the disease was ready for assessment. The period betweeninoculation and assessment varied from four to fourteen days accordingto the disease and environment.

The disease control was recorded by the following grading:

4=no disease

3=trace--5% of disease on untreated plants

2=6-25% of disease on untreated plants

1=26-59% of disease on untreated plants

0=60-100% of disease on untreated plants

The results are shown in Tables VI-IX .

                                      TABLE VI                                    __________________________________________________________________________                                 PYRI-   CERCOSPORA                               COM-  PUCCINIA                                                                              ERYSIPHE                                                                             VENTURIA                                                                              CULARIA ARACHI- PLASMOPARA                                                                            PHYTOPHTHORA             POUND RECONDITA                                                                             GRAMINIS                                                                             INAEQUALIS                                                                            ORYZAE  DICOLA  VITICOLA                                                                              INGESTANS                NUMBER                                                                              (WHEAT) (BARLEY)                                                                             (APPLE) (RICE)  (PEANUT)                                                                              (VINE)  (TOMATO)                 __________________________________________________________________________    1     4       0      4       4       4       4       --                       2     4       4      4       4       2       4       --                       3     0       4      4       3       4       4       --                       9     0       0      2       0       0       2       --                       10    3       4      3       3       4       4       --                       11    4       4      --      4       4       4       --                       12    2       0      1       0       0       4       --                       13    3       3      4       4       4       4       --                       14    4       4      4       4       4       4       --                       15    4       4      --      4       3       4       --                       16    0       0      1       0       0       0       --                       18    0       1      1       0       0       0       --                       20    4       4      4       4       4       4       --                       21    2       4      4       0       4       0       --                       22    3       4      4       3       0       4       --                       23    3       4      4       4       4       4       --                       24    4       4      4       4       4       4       --                       25    2       4      2       3       4       4       --                       26    0       1      2       0       4       0       --                       27    4       4      4       4       4       4       --                       28    4       4      4       4       4       4       3                        29    4       4      4       4       4       4       --                       30    4       4      4       3       4       4       2                        34                                                                            40                                                                            __________________________________________________________________________

                                      TABLE VIII                                  __________________________________________________________________________                                 PYRI-   CERCOSPORA                               COM-  PUCCINIA                                                                              ERYSIPHE                                                                             VENTURIA                                                                              CULARIA ARACHI- PLASMOPARA                                                                            PHYTOPHTHORA             POUND RECONDITA                                                                             GRAMINIS                                                                             INAEQUALIS                                                                            ORYZAE  DICOLA  VITICOLA                                                                              INGESTANS                NUMBER                                                                              (WHEAT) (BARLEY)                                                                             (APPLE) (RICE)  (PEANUT)                                                                              (VINE)  (TOMATO)                 __________________________________________________________________________    1     1       0      0       0       --      0       --                       __________________________________________________________________________

                                      TABLE IX                                    __________________________________________________________________________                                 PYRI-   CERCOSPORA                               COM-  PUCCINIA                                                                              ERYSIPHE                                                                             VENTURIA                                                                              CULARIA ARACHI- PLASMOPARA                                                                            PHYTOPHTHORA             POUND RECONDITA                                                                             GRAMINIS                                                                             INAEQUALIS                                                                            ORYZAE  DICOLA  VITICOLA                                                                              INGESTANS                NUMBER                                                                              (WHEAT) (BARLEY)                                                                             (APPLE) (RICE)  (PEANUT)                                                                              (VINE)  (TOMATO)                 __________________________________________________________________________    1     4       3      4       4       4       4       --                       2     0       0      4       0       4       0       --                       3     0       3      1       0       0       0       --                       5     4       4      4       4       4       3       3                        6     0       0      4       0       0       3       --                       7     1       0      4       3       4       3       2                        8     2       0      4       4       4       3       0                        15    0       0      0       0       0       3       0                        18    1       0      0       0       4       2       0                        __________________________________________________________________________     -- means not tested                                                      

We claim:
 1. A compound of formula: ##STR15## or a stereoisomer thereof,wherein W, X and Y are independently hydrogen, halogen, nitro, cyano,C₁₋₄ alkyl, C₃₋₆ alkenyl, C₃₋₆ alkynyl, C₁₋₄ alkoxy, amino, COOR³, CONR³R⁴, COR³, S(O)_(n) R³ or CR³ ═NR⁴, where R³ and R⁴ are hydrogen or C₁₋₄alkyl and n is 0, 1 or 2; Z is COOR', CONR'R" or COR', were R" ishydrogen or C₁₋₄ alkyl, R' is thienyl which is optionally substitutedwith C₁₋₄ alkyl, C₁₋₄ alkoxy, halogen, halo(C₁₋₄)alkyl, C₃₋₆ cycloalkyl,C₃₋₆ cycloalkenyl, phenyl, cyano or nitro; and V is oxygen or sulphur.2. A compound according to claim 1 wherein Z is COR' and R' is thienyloptionally substituted with C₁₋₄ alkyl, C₁₋₄ alkoxy, halogen,halo(C₁₋₄)alkyl, C₃₋₆ cycloalkyl, C₃₋₆ cycloalkenyl, phenyl, cyano ornitro.
 3. A fungicidal composition comprising, as an active ingredient,a fungicidally effective amount of a compound of general formula I asdefined in claim 1, together with a carrier therefor.
 4. A process forcombating fungi which comprises applying to a plant, to seed of a plant,or to the locus of the plant or seed, a fungicidally effective amount ofa compound as defined in claim 1 or a composition containing the same.5. A compound of formula: ##STR16## wherein Z is theinylcarbonyl; and Yis hydrogen, C₁₋₄ alkyl or nitro.
 6. A compound of formula: ##STR17## inwhich W, X and Y are independently hydrogen, halogen, nitro, cyano, C₁₋₄alkyl, C₃₋₆ alkenyl, C₃₋₆ alkynyl, C₁₋₄ alkoxy, amino, COOR³, CONR³ R⁴,COR³, S(O)_(n) R³ or CR³ ═NR⁴, where R³ and R⁴ are hydrogen or C₁₋₄alkyl and n is 0, 1 or 2; Z is COOR', CONR'R" or COR', where R" ishydrogen or C₁₋₄ alkyl, R' is thienyl, which is optionally substitutedwith C₁₋₄ alkyl, C₁₋₄ alkoxy, halogen, halo(C₁₋₄)alkyl, C₃₋₆ cycloalkyl,C₃₋₆ cycloalkenyl, phenyl, cyano or nitro.